Electro-oxidative coupling of Bunte salts with aryldiazonium tetrafluoroborates: a benign access to unsymmetrical sulfoxides.

An electrochemical strategy for the synthesis of unsymmetrical sulfoxides has been explored using Bunte salts and aryldiazonium tetrafluoroborates under constant current electrolysis at room temperature. In addition to being eco-safe and using mild conditions, the present protocol is free from the use of metal/oxidant, and is endowed with a broad substrate scope and good functional group tolerance.

Synthesis of unsymmetrical ketones via dual catalysed cross-coupling of α,ß-unsaturated carboxylic acids with aryldiazonium salts.

A visible light-enabled synthesis of unsymmetrical ketones has been accomplished by the cross-coupling of α,ß-unsaturated carboxylic acids and aryldiazonium salts embracing a synergistic eosin Y and Co(OAc)2·4H2O catalysis. The reaction involves decarboxylative aerobic CC bond cleavage, and is endowed with the creation of new C-C and C-O bonds with good substrate scope.

Whole chloroplast genome-specific non-synonymous SNPs reveal the presence of substantial diversity in the pigeonpea mini-core collection.

To unravel the plastid genome diversity among the cultivated groups of the pigeonpea germplasm, we characterized the SNP occurrence and distribution of 142 pigeonpea mini-core collections based on their reference-based assembly of the chloroplast genome. A total of 8921 SNPs were found, which were again filtered and finally 3871 non-synonymous SNPs were detected and used for diversity estimates. These 3871 SNPs were classified into 12 groups and were present in only 44 of the 125 genes, demonstrating the presence of a precise mechanism for maintaining the whole chloroplast genome throughout evolution. The Acetyl-CoA carboxylase D gene possesses the maximum number of SNPs (12.29%), but the Adenosine Tri-Phosphate synthatase cluster genes (atpA, atpB, atpE, atpF, atpH, and atpI) altogether bear 43.34% of the SNPs making them most diverse. Various diversity estimates, such as the number of effective alleles (1.013), Watterson's estimate (0.19), Tajima's D ( - 3.15), Shannon's information index (0.036), suggest the presence of less diversity in the cultivated gene pool of chloroplast genomes. The genetic relatedness estimates based on pairwise correlations were also in congruence with these diversity descriptors and indicate the prevalence of rare alleles in the accessions. Interestingly, no stratification was observed either through STRUCTURE, PCoA, or phylogenetic analysis, indicating the common origin of the chloroplast in all the accessions used, irrespective of their geographical distribution. Further 6194 Cleaved Amplified Polymorphic Sequences (CAPS) markers for 531 SNPs were developed and validated in a selected set of germplasm. Based on these results, we inferred that all of the cultivated gene pools of pigeonpea have a common origin for the chloroplast genome and they possess less diversity in protein-coding regions, indicating a stable and evolved plastid genome. At the same time, all diversity analysis indicates the occurrence of rare alleles, suggesting the suitability of the mini-core collection in future pigeonpea improvement programs. In addition, the development of chloroplast genome-based CAPS markers would have utility in pigeonpea breeding programs. Supplementary Information: The online version contains supplementary material available at 10.1007/s13205-023-03785-8.

Synthesis of functionalized alkenes via Cu(I)-catalysed allylation of acetanilides using Morita-Baylis-Hillman bromides.

An easy access to functionalized alkenes has been developed by the C-H functionalization of anilides with Morita-Baylis-Hillman (MBH) bromides in the presence of copper chloride, TBHP and acetic acid. Unsubstituted as well as ortho/meta-substituted anilides exclusively give rise to the para-allylated products, whereas para-substitution brings about the formation of ortho-allylated anilides.

Visible-Light-Mediated Synthesis of α-Ketoamides via Oxidative Amination of 2-Bromoacetophenones Using Eosin Y as a Photoredox Catalyst.

An oxidative amination of 2-bromoacetophenones has been accomplished to provide α-ketoamides by using photoredox catalysis with air as oxidant. The reactants are readily accessible, and the method is endowed with broad substrate scope and good functional group tolerance. The practicality of the approach is also shown by a gram-scale reaction.

A regioselective synthesis of ß-difluoromethoxy vinyl sulfones via O-difluoromethylation of ß-ketosulfones using sodium chlorodifluoroacetate.

A practical synthesis of new ß-difluoromethoxy vinyl sulfones has been explored by O-difluoromethylation of ß-ketosulfones using the inexpensive and easily workable sodium chlorodifluoroacetate as a difluorocarbene precursor. The strategy is convenient and regioselective, and features an adequate substrate scope and functional group tolerance.

Easy access to α-carbonyl sulfones using cross-coupling of α-aryl-α-diazoesters with sulfonyl hydrazides.

A facile synthesis of α-carbonyl sulfones has been accomplished by the cross-coupling of α-aryl-α-diazoesters with sulfonyl hydrazides in the presence of CuI and DBU. The reaction employs inexpensive and bench stable sulfonyl hydrazides as a sulfonyl source, and facilitates the migratory insertion with α-aryl-α-diazoesters under mild reaction conditions.

Copper-Catalyzed Thiolation of Hydrazones with Sodium Sulfinates: A Straightforward Synthesis of Benzylic Thioethers.

A facile and sustainable protocol for the thiolation of hydrazones with sodium sulfinates has been developed in the presence of CuBr2 and DBU in DMF to afford diverse benzylic thioethers. Control experiments reveal a radical pathway involving a thiyl radical as a key intermediate.

Exploring genetic diversity and ascertaining genetic loci associated with important fruit quality traits in apple (Malus × domestica Borkh.).

Genetic diversity is the primary source of variability in any crop improvement program, and the diverse germplasm of any crop species represents an important genetic resource for gene or allele mining to meet future needs. Huge genetic and phenotypic diversity is present in the apple gene pool, even though, breeding programs have been mainly focused on a few traits of interests, which have resulted in the reduction of the diversity in the cultivated lines of apple. Therefore, the present study was carried out on 70 diverse apple genotypes with the objective of analyzing the genetic diversity and to identify the genetic loci associated with important fruit quality traits. A total of 140 SSR primers were used to characterize the 70 genotypes of apples, out of which only 88 SSRs were found to be polymorphic. The PIC values varied from 0.03 to 0.75. The value of MI, EMR, and RP varied from 0.03 to 3.5, 0.5 to 5.0, and 1.89 to 6.74, respectively. The dendrogram and structure analysis divided all the genotypes into two main groups. In addition to this, large phenotypic variability was observed for the fruit quality traits under study indicated the suitability of the genotypes for association studies. Altogether 71 novel MTAs were identified for 10 fruit quality traits, of which 15 for fruit length, 15 for fruit diameter, 12 for fruit weight, 2 for total sugar, 2 for TSS, 4 for reducing sugar, 5 for non-reducing sugar, 5 for fruit firmness, 5 for fruit acidity and 6 for anthocyanin, respectively. Consistent with the physicochemical evaluation of traits, there was a significant correlation coefficient among different fruit quality characters, and many common markers were found to be associated with these traits (fruit diameter, length, TSS, total sugar, acidity and anthocyanin, respectively) by using the different modeling techniques (GLM, MLM). The inferred genetic structure, diversity pattern and the identified MTAs will be serving as resourceful grounds for better predictions and understanding of apple genome towards efficient conservation and utilization of apple germplasm for facilitating genetic improvement of fruit quality traits. Furthermore, these findings also suggested that association mapping could be a viable alternative to the conventional QTL mapping approach in apple. Supplementary Information: The online version contains supplementary material available at 10.1007/s12298-023-01382-w.

A convenient synthesis of N-(hetero)arylamides by the oxidative coupling of methylheteroarenes with amines.

An oxidative amidation of 2-methylpyridines/2-methylbenzimidazole with amines using copper acetate and elemental sulfur in DMSO to afford various N-(hetero)arylamides has been accomplished. Mechanistic studies reveal the intermediacy of N-(pyridin-2-ylmethyl)aniline and confirm the role of DMSO as the oxygen source.

Visible-Light Photoredox-Catalyzed Synthesis of trans-Oxiranes via Decarboxylative Stereospecific Epoxidation of trans-Cinnamic Acids by Aryldiazonium Salts.

An efficient visible-light-induced synthesis of trans-oxiranes has been accomplished via decarboxylative stereospecific epoxidation of trans-cinnamic acids by aryldiazonium salts using CuCl, eosin Y, TBHP, and DBU. The reaction is facile, straightforward, and endowed with good functional group tolerability and a good substrate scope.

Visible-Light-Induced Photocatalytic Trifluoromethylation of Bunte Salts: Easy Access to Trifluoromethylthiolated Synthons.

A metal-free visible-light-induced trifluoromethylation of Bunte salts of α-bromoketones/alkyl bromide/benzyl bromides/functionalized allyl (Baylis-Hillman) bromides has been accomplished using Langlois' reagent in the presence of inexpensive eosin Y as a photocatalyst to form the privileged trifluoromethylthiolated synthons. The method is straightforward, operationally simple, and endowed with broad substrate scope and good functional group tolerance.

Identification of significant marker-trait associations for Fusarium wilt resistance in a genetically diverse core collection of safflower using AFLP and SSR markers.

Safflower (Carthamus tinctorius L.), an oilseed crop, is severely affected by Fusarium oxysporum f. sp. carthami (Foc), a fungus causing Fusarium wilt (FW) resulting in up to 80% yield loss. In the present study, we used a panel of 84 diverse accessions from the composite core collection to perform association mapping for FW-resistance. Hydroponics-based screening resulted in categorization of 84 accessions as 31 immune, 19 highly resistant, 9 moderately resistant, 4 moderately susceptible, and 21 highly susceptible. Genotyping with a combination of 155 AFLP and 144 SSR markers revealed substantial genetic differentiation and structure analysis identified three main subpopulations (K = 3) with nearly 35% of admixtures in the panel. Kinship analysis at individual and population level revealed absence of or weak relatedness between the accessions. Association mapping with General Linear Model and Mixed Linear Model identified 4 marker-trait associations (MTAs) significantly linked with the FW-resistance trait. Of these, 3 robust MTAs identified in both the models exhibited phenotypic variance ranging from 4.09 to 6.45%. Locus-128 showing a low P-value and high phenotypic variance was identified as a promising marker-trait association that will facilitate marker-assisted breeding for FW-resistance in safflower.

Visible-Light-Induced Photocatalytic Synthesis of ß-Keto Dithiocarbamates via Difunctionalization of Styrenes.

A facile photocatalyzed strategy for difunctionalization of styrenes in the presence of CS2 and amines providing ß-keto dithiocarbamates has been developed. In the case of 4-nitrostyrene and 2-vinylpyridine, however, only 2-arylethylthiocarbamates are interestingly formed without the aid of photoredox catalysis/TBHP.

Iodine-catalyzed thioallylation of indoles using Bunte salts prepared from Baylis-Hillman bromides.

Metal-free iodine-catalyzed regioselective thioallylation of indoles has been accomplished at room temperature using Bunte salts prepared from Baylis-Hillman bromides. The resulting multi-functional C3 thioallylated indoles exhibit ample structural diversity and good functional group tolerance.

Visible-Light-Induced Photocatalytic Oxidative Decarboxylation of Cinnamic Acids to 1,2-Diketones.

A concerted metallophotoredox catalysis has been realized for the efficient decarboxylative functionalization of α,ß-unsaturated carboxylic acids with aryl iodides in the presence of perylene bisimide dye to afford 1,2-diketones.

Metal-free multicomponent reactions: a benign access to monocyclic six-membered N-heterocycles.

The advent of multicomponent reactions in the synthesis of heterocycles and their ever burgeoning applications in drug development, materials chemistry, and catalysis, have attracted a great deal of current scientific interest. In particular, the metal-free multicomponent synthesis of six membered N-heterocycles has undergone intensive research over the last two decades offering an environmentally benevolent means contrary to traditional metal catalysed reactions. To the best of our knowledge, there exists no exclusive review on the metal-free multicomponent synthesis of six membered N-heterocyles, and hence the present report highlights the progress on metal-free multicomponent reactions with their advantages and mechanistic insights to access monocyclic six-membered N-heterocycles including pyridine, pyrimidine, pyrazine, triazine and their hydrogenated derivatives. The literature is covered since 2000, and the contents offer not only striking methods for divergent synthesis of six-membered N-heterocycles but also put forward some new insights into the exploration of metal-free multicomponent chemistry.

Iron-Catalyzed Radical Activation Mechanism for Denitrogenative Rearrangement Over C(sp3 )-H Amination.

An iron-catalyzed denitrogenative rearrangement of 1,2,3,4-tetrazole is developed over the competitive C(sp3 )-H amination. This catalytic rearrangement reaction follows an unprecedented metalloradical activation mechanism. Employing the developed method, a wide number of complex-N-heterocyclic product classes have been accessed. The synthetic utility of this radical activation method is showcased with the short synthesis of a bioactive molecule. Collectively, this discovery underlines the progress of radical activation strategy that should find wide application in the perspective of medicinal chemistry, drug discovery and natural product synthesis research.

Iodine-Catalyzed Synthesis of 3-Arylthioindoles Employing a 1-Aryltriazene/CS2 Combination as a New Sulfenylation Source.

A practical approach for the regioselective synthesis of 3-arylthioindoles has been accomplished using a combination of 1-aryltriazene/CS2 as a new sulfenylation source. The methodology employs molecular iodine as a catalyst and is compatible with a variety of structurally diverse reactants.